0000000000056458
AUTHOR
Kaspars Traskovskis
Carbene-metal complexes as molecular scaffolds for construction of through-space TADF emitters
Through-space charge transfer (CT) process is observed in Cu(I) carbene-metal-amide complexes, where conventional imidazole or imidazoline N-heterocyclic (NHC) carbene fragments act as inert linkers and CT proceeds between a metal-bound carbazole donor and a distantly situated carbene-bound phenylsulfonyl acceptor. The resulting electron transfer gives a rise to efficient thermally activated delayed fluorescence (TADF), characterized with high photoluminescence quantum yields (ΦPL up to 90 %) and radiative rates (kr) up to 3.32×105 s-1. TADF process is aided by fast reverse intersystem crossing (rISC) rates of up to 2.56×107 s-1. Such emitters can be considered as hybrids of two existing TA…
Triphenyl moieties as building blocks for obtaining molecular glasses with nonlinear optical activity
The incorporation of trityl and triphenylsilyl groups into low molecular weight molecules allows the formation of stable molecular glasses. A series of materials based on the N-phenyldiethanolamine core was synthesized bearing different azobenzenes and benzylydene-1,3-indandione as active chromophores. Molecular hyperpolarizability of the synthesized compounds was calculated by a restricted Hartree–Fock method with basis 6-31G(d,p) and measured in solutions by hyper-Rayleigh scattering. Non-linear optical (NLO) activity of the thin glassy films was confirmed after a corona poling procedure. Thermal sustainability of the NLO response of up to 85 °C was achieved. Quantum chemical calculations…
Photoinduced mass transport in low molecular organic glasses and its practical application in holography
Abstract In this paper we present the synthesis and optical properties of amorphous low molecular compound 4-((4-(bis(5,5,5-Triphenylpentyl)amino)phenyl)diazenyl)benzoic acid. The surface relief gratings formation by polarization holography method on these thin films (thicknesses are 200–1700 nm) was shown. The dependence of the surface relief modulation on various parameters: recording exposure dose, the polarization state of the recording beams, the grating period and the film thickness of the material was demonstrated. Values of surface tension at the air-film before and after irradiation of the substance by polarized radiation were measured. The efficiency of surface relief formation in…
Triphenylmethyl and triphenylsilyl based molecular glasses for photonic applications
Triphenylmethyl and triphenylsilyl structural fragments can be used to obtain glass forming, solution processable materials from polar chromophore molecules. Large number of compounds has been synthesized taking advantage of this approach, making it possible to identify some structure-property relations. Regarding the non-linear optical (NLO) properties of the given materials it is evident that triphenylmethyl groups help shielding unwanted NLO efficiency limiting dipolar interactions between polar chromophores in solid films. Chromophore stacking is still observed for compounds with large dipole momentum values. The glass transition temperatures of the compounds increase with the molecular…
All-organic fast intersystem crossing assisted exciplexes exhibiting sub-microsecond thermally activated delayed fluorescence
A novel strategy is presented towards acquisition of exciplex systems exhibiting thermally activated delayed fluorescence (TADF) with a high reverse intersystem crossing (RISC) rate (exceeding 107 s−1). This approach involves constructing exciplex donor–acceptor molecular pairs, where the acceptor molecule possesses the ability to undergo fast and efficient intersystem crossing (ISC). With the use of 6-cyano-9-phenylpurine (PCP) acceptor and carbazole-based donor molecules, exciplexes were obtained, where the excitation is contained on PCP and undergoes fast ISC to form a local excited triplet state (3LEA). The controlled excitation transfer to the 3LEA level provides an optimal reverse int…
Modular approach to obtaining organic glasses from low-molecular weight dyes using 1,1,1-triphenylpentane auxiliary groups: Nonlinear optical properties
Abstract A new modular synthetic approach to obtain organic glasses from low-molecular weight azobenzenes and stilbenes has been accomplished using 1,1,1-triphenylpentane crystallization preventing auxiliary groups. Six new structures show excellent solubility in non-polar solvents and thin films with good optical qualities have been obtained using a spin-coating technique. The glass transition temperatures of the new amorphous materials were in the range of 73–108 °C. The nonlinear optical activity in thin amorphous films was measured after a corona poling procedure.
Synthesis and Photoelectrical Properties of 3-(Diphenylamino)Carbazolyl-Functionalized DMABI Derivatives
A modular approach was used in the synthesis of the 3-(diphenylamino)carbazolyl- functionalized 2-(4-(dimethylamino)benzylidene)-1H-indene-1,3(2H)-dione (DMABI) derivatives. For this purpose, carboxyl functional group was introduced into the framework of DMABI molecule. Additionally, a regioselective method for substitution of carbonyl group of DMABI with dicyanomethylene group was investigated and verified using the heteronuclear multiple bond correlation NMR spectra. Steglich esterification method was used to connect the 3‑(diphenylamino)carbazolyl moiety via an unconjugated spacer. The UV-Vis absorption spectra and molecular energy level data were obtained for the evaluation of the synth…
Solution-processable green phosphorescent iridium(III) complexes bearing 3,3,3-triphenylpropionic acid fragment for use in OLEDs
New solution-processable materials based on well-known green iridium(III) heteroleptic complexes (ppy) 2 Ir(acac) and (ppy) 2 Ir(pic) were acquired by chemical modification of ppy ligand with functionable hydroxyl groups and subsequent esterification with 3,3,3-triphenylpropionic acid fragment. Photoluminescence quantum efficiencies up to 0.90 were measured for the compounds in solution. Emission characteristics in pure solid films and different guest-host systems with hole transporting materials were investigated. Green light emitting OLEDs (organic light emitting devices) was prepared and characterized.
Effects of steric encumbrance of iridium( iii ) complex core on performance of solution-processed organic light emitting diodes
Iridium(iii) complexes are the most frequently applied commercialized green and red emitters for organic light emitting diode (OLED) displays. Throughout years a significant research effort has been devoted to modify these compounds, in order to make them suitable for cost-effective solution-processing techniques, such as inkjet printing. To achieve this, the inherent tendency of the complex molecules to form poorly emissive aggregates needs to be suppressed. In many cases this has been achieved by an encapsulation of the iridium(iii) complex core with dendritic structures, composed of either passive or charge-transporting fragments. In order to validate this approach, we acquired three str…
Stereoselective synthesis and properties of 1,3-bis(dicyanomethylidene)indane-5-carboxylic acid acceptor fragment containing nonlinear optical chromophores
A series of organic push–pull type chromophores using indane-1,3-dione 5-carboxylic acid (IDCA) and novel 1,3-bis(dicyanomethylidene)indane 5-carboxylic acid (CICA) electron acceptor fragments have been synthesized and characterized. NMR and X-ray analysis revealed that condensation reactions with the CICA fragment were stereoselective and yielded benzylidenes and azomethines with E double bond configurations. Due to the non-planar geometry these compounds are chiral and were acquired as a racemic mixture. The subsequent functionalization of the carboxylic acid group with 5,5,5-triphenylpentan-1-ol yielded solution-processable glass forming materials (6, 8, 10, 13) with glass transition tem…
Nonlinear optical properties of low molecular organic glasses formed by triphenyl modified chromophores
The series of organic molecular glasses have been studied as possible candidates for nonlinear optical (NLO) applications. Amorphous phase formation of investigated materials is ensured by the presence of bulky triphenyl substituents in molecular structure of NLO chromophores. Linear optical properties as well as NLO coefficients and thermal stability of NLO activity for the 13 molecular materials in glassy thin solid films have been determined. For the benzylidene-1,3-indandione chromophore containing compound the highest d33 value equal to 280 pm/V was measured under the 1064 nm excitation. Among the investigated compounds uppermost achieved thermal sustainability of NLO response was 108 …
Eu3+ ternary and tetrakis complexes with carbazole and methyl group substituted dibenzoylmethane derivatives: Induction of aggregation enhanced emission
Abstract Two dibenzoylmethane (DBM) derivatives with methyl (Me-DBM) or carbazole (CBZ-DBM) substituents at the para-position of the phenyl ring and their four novel ternary and tetrakis Eu3+ complexes with 1,10-phenanthroline (PHEN) as a secondary ligand or tetraethylamonium ion (N+(Et)4) as the counter-cation were synthesized and characterized. The investigation of the optical properties of the complexes revealed that Me-DBM based compounds exhibit aggregation enhanced emission (AEE), while in the case of CBZ-DBM this effect is not observed. At the same time, the introduction of a carbazole substituent reduces the emission quantum yield of the complexes. The decrease in luminescence effic…
Unusual response to environmental polarity in a nonlinear-optical benzylidene-type chromophore containing a 1,3-bis(dicyanomethylidene)indane acceptor fragment.
One of the strongest known electron-accepting fragments used in the synthesis of organic dyes for applications in nonlinear optics (NLO) is 1,3-bis(dicyanomethylidene)indane (BDMI). By studying a benzylidene-type push-pull chromophore bearing a 5-carboxy-BDMI electron-acceptor and 4-(dimethylamino)aniline donor fragment, we demonstrate that this class of compounds can show unusual response to the polarity of the surrounding medium. The combined results of UV-Vis absorption spectrometry, NMR experiments and computational modeling indicate that the studied compound undergoes a geometrical transformation that involves an increase in the torsion angle ω between the aniline and indane ring syste…
Structure-dependent tuning of electro-optic and thermoplastic properties in triphenyl groups containing molecular glasses
Abstract The series of seven molecular compounds composed of D–π–A chromophores and triphenylmethyl auxiliary groups were characterized by UV–Vis spectroscopy, differential scanning calorimetry and quantum chemical calculations. Nonlinear optical (NLO) properties of compounds were determined by second harmonic generation measurements in corona poled thin glassy films. The results show that triphenylmethyl auxiliary groups are effective at shielding undesirable dipole interactions in solid phase thus increasing NLO efficiency of materials. Thermal stability up to 108 °C was achieved for a polar order in poled samples.
An improved molecular design of obtaining NLO active molecular glasses using triphenyl moieties as amorphous phase formation enhancers
New molecular design of obtaining molecular glasses has been developed by linking triphenylmethyl moieties to chromophore core by flexible C-C bridge. Compounds capable of forming stable amorphous phase with good optical quality have been acquired with increased chemical and thermal sustainability compared to the previously reported design. NLO activity of compounds has been measured after corona discharge polling. Compared to previously synthesized trityloxy fragment containing compounds increase of d 33 coefficient by up to 17 times was achieved for the same chromophore core containing compounds.
Synthesis and investigation of charge transport properties in adducts of hole transporting carbazole derivatives and push-pull azobenzenes
Abstract In order to investigate the viability of a material design for bulk heterojunction (BHJ) organic solar cells, where hole transporting group is bound to the donor moiety, we report the synthesis and charge transport characteristics of 3-(diphenylamino)carbazolyl-functionalized derivatives of 2-(4-((4-(dimethylamino)phenyl)diazenyl)benzylidene)-1H-indene-1,3-dione (DMAAzi) chromophore. Three different bounding configurations were examined in these adducts. Additionally, a trityl-functionalized derivative of DMAAzi was prepared and used for comparison purposes. All of the synthesized materials form thin amorphous films from volatile organic solvents and exhibit glass transition temper…
Synthesis and nonlinear optical properties of novel N,N-dihydroxyethyl-based molecular organic glasses using triaryl substitutes as amorphous phase formation enhancers
In given study a new structural design of molecular NLO materials is presented where amorphous phase formation is achieved by introduction of bulky trityl and triphenylsilyl substituents. Obtained materials formed stable organic glasses with good optical quality and glass transition temperatures notably exceeding ambient. NLO activity was successfully measured in samples that underwent corona discharge poling. The comparison of both enhancer groups revealed, that trityl group increases thermal sustainability of material, while triphenylsilyl group better promotes formation and stability of amorphous phase.
3,3'-Bicarbazole structural derivatives as charge transporting materials for use in OLED devices
In this study we report novel 3,3′-bicarbazole based charge transporting materials mainly designed for a use in systems containing phosphorescent iridium (III) complex emitters. A low-cost oxidative coupling reaction using FeCl3 was employed in the synthesis of 3,3′-bicarbazole compounds. Different derivatives of 3,3′-bicarbazole with 4-ethoxyphenyland ethyl- substituents at 9,9′- positions and (2,2-diphenylhydrazono)methyl- and 4-(dimethylamino)styryl- substituents at 6,6′- positions were synthesized. Obtained (2,2-diphenylhydrazono)methyl- derivatives exhibit glass transition temperatures that are sufficient for applications in electronic devices. Thin amorphous films of good optical qual…
Emission Enhancement by Intramolecular Stacking between Heteroleptic Iridium(III) Complex and Flexibly Bridged Aromatic Pendant Group
Phosphorescent iridium(III) complexes suffer from a strong aggregation quenching, limiting their use in solution-processed or crystalline organic light-emitting diodes. Here we report how an intramolecular stacking between a flexibly bridged bulky aromatic pendant group and the core of nonionic heteroleptic complex can be exploited to minimize the negative effects of this drawback. The stacked conformation provides a rigid sterical shielding of the polar molecular surface, improving photoluminescence quantum yield of the complex both in solution and crystalline state.
Photophysical and Electrical Properties of Highly Luminescent 2/6-Triazolyl-Substituted Push-Pull Purines.
This work is supported by the ERDF 1.1.1.1. activity project No. 1.1.1.1/16/A/131. The authors thank Dr. sc. ing. Jānis Zicāns and Dr. sc. ing. Remo Merijs Meri for DSC analyses.
Thiphenylmethane based structural fragments as building blocks towards solution-processable heteroleptic iridium(iii) complexes for OLED use
A novel structural approach to solution-processable heteroleptic iridium(III) complexes is presented. On the basis of 2-arylbenzo[d]thiazole cyclometalating main ligands and picolinic acid (pic) and acetylacetone (acac) ancillary ligands six new yellow or orange emitting materials were obtained using attached 1,1,1-triphenylmethylpentane substituents as aggregation preventing and solubility enhancing functional fragments. The obtained compounds show high photoluminescence quantum yield values in the range of 0.64 to 0.90. OLEDs with a spin-coated emissive layer were successfully prepared, with the highest achieved external quantum efficiency of 7.9%, current efficiency of 12.4 cd A−1 and po…
CCDC 1988182: Experimental Crystal Structure Determination
Related Article: Kaspars Traskovskis, Armands Sebris, Irina Novosjolova, Māris Turks, Matas Guzauskas, Dmytro Volyniuk, Oleksandr Bezvikonnyi, Juozas V. Grazulevicius, Anatoly Mishnev, Raitis Grzibovskis, Aivars Vembris|2021|J.Mater.Chem.C|9|4532|doi:10.1039/D0TC05099G
CCDC 1845861: Experimental Crystal Structure Determination
Related Article: Kaspars Traskovskis, Valdis Kokars, Sergey Belyakov, Natalija Lesina, Igors Mihailovs, Aivars Vembris|2019|Inorg.Chem.|58|4214|doi:10.1021/acs.inorgchem.8b03273
CCDC 1436954: Experimental Crystal Structure Determination
Related Article: Kaspars Traskovskis, Valdis Kokars, Andrejs Tokmakovs, Igors Mihailovs, Edgars Nitiss, Marina Petrova, Sergey Belyakov, Martins Rutkis|2016|J.Mater.Chem.C|4|5019|doi:10.1039/C6TC00203J